CN114122258A - Celestite blue film composite material and preparation method thereof - Google Patents

Celestite blue film composite material and preparation method thereof Download PDF

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CN114122258A
CN114122258A CN202111355127.1A CN202111355127A CN114122258A CN 114122258 A CN114122258 A CN 114122258A CN 202111355127 A CN202111355127 A CN 202111355127A CN 114122258 A CN114122258 A CN 114122258A
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celestite
layer
blue
film
composite material
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张程
李阳
马春兰
何瑞钰
施智明
刘娇
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Suzhou University of Science and Technology
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Abstract

The invention belongs to the field of composite materials, and particularly relates to a celestite blue film composite material and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving celestite blue in a mixed solvent to obtain a precursor solution for preparing the film; injecting the solution into an electrolytic cell, applying direct current voltage, and depositing the celestite blue material on the interface of the conductive electrode to obtain a layer of uniform nano fibrous self-assembled film; and after vacuum drying, plating a layer of metal Al electrode on the surface of the functional material film to serve as a top electrode, and using the deposited conductive electrode as a bottom electrode to prepare the celestite blue film composite material. The invention effectively realizes the preparation of the organic nanofiber self-assembled film by utilizing the functional groups of the material and the external electric field acting force, effectively improves the electrical characteristics of the material, induces the storage effect based on electric signal response, and has reliable application prospect in the field of electric memories.

Description

Celestite blue film composite material and preparation method thereof
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a celestite blue film composite material and a preparation method thereof.
Background
The twenty-first century is the era of science and technology, social development is changing day by day, and people are more and more oriented to convenient life brought by intellectualization. However, the back of intelligent development is derived from the powerful support of hardware devices on the one hand and the rapid development of "big data" and its storage technology on the other hand. The daily data processing amount of the current society is increased in the number of geometric series, and the requirement of the society on a memory is higher and higher. Therefore, the safe, efficient and large-capacity storage of data becomes the leading soldier in the 'big data' era. Organic electric information storage materials and nanometer devices with binary or even multilevel information storage functions become hot spots for research of scientists. The organic nano-fiber is widely researched in the field of constructing organic nano-devices, and the advantages of the organic nano-fiber are mainly shown in the following aspects: 1. compared with a body structure, the nanofiber has more excellent mechanical properties and has greater development potential in the field of flexible organic electronic devices; 2. the nanofiber can form a stable electron transmission channel along the long axis and the diameter direction, so that the nanofiber has excellent electrical properties.
To date, researchers have explored diverse physicochemical strategies to synthesize nanofibers of conjugated materials, including spontaneous thermodynamic and kinetic methods (e.g., thermal evaporation, solvothermal, sol-gel, chemical vapor deposition, etc.) as well as external force-assisted methods (e.g., template-assisted, magnetic field-assisted). However, the above methods all have certain limitations, for example, the thermal evaporation method has high energy consumption and low controllability; the process flow of the external acting force auxiliary method is complicated; conventional film-forming methods (such as spin coating and vacuum evaporation) produce non-equilibrium morphology due to solvent evaporation or rapid quenching due to thermal effects of the film, which is not conducive to obtaining uniform self-assembled segments of nanofibers on the substrate. Furthermore, the above problems all pose great challenges for preparing large-area and homogeneous organic nanofiber thin films. Therefore, the size-controllable nanofiber film is synthesized in an organic solvent by utilizing an electric induction deposition process, and an oriented self-assembly stacking mode is formed on the substrate interface under the action of external electric field force, so that the method has important significance for improving the performance of the electric storage information device.
Disclosure of Invention
The invention aims to provide a celestite blue film composite material, and the preparation method of the celestite blue film composite material not only effectively enhances the compactness of the accumulation between organic functional material molecules and the ductility of a film, but also can ensure the realization of the transfer process of charges in molecules, induce the resistance state change based on electric signal response, and realize the storage and the erasure of information. Meanwhile, the application of the celestite blue film composite material in the field of information storage is provided.
The invention provides a preparation method of a celestite blue film composite material, which comprises the following steps:
(1) dissolving celestite blue in dimethyl sulfoxide, adding acetonitrile to obtain precursor solution,
(2) depositing the precursor solution on a conductive substrate to form a fiber film layer;
(3) and sequentially evaporating a fluoride layer and a top electrode layer on the surface of the fiber film layer to obtain the celestite blue film composite material.
Preferably, in the step (1), the temperature for mixing the dimethyl sulfoxide and the acetonitrile is 20-30 ℃ and the time is 8-16 h.
Preferably, in the step (1), the volume ratio of dimethyl sulfoxide to acetonitrile is 1: 8-10.
Preferably, in the step (1), the concentration of celestite blue in the precursor solution is 0.1-0.3 mg/mL.
Preferably, the conductive substrate is an Indium Tin Oxide (ITO) layer substrate or a zinc oxide (FTO) layer substrate; the fluoride layer is a lithium fluoride layer or a magnesium fluoride layer; the top electrode layer is a metal Au layer, an Ag layer or an Al layer.
Preferably, the specific operation of step (2) is as follows: and placing the precursor solution in an electrolytic cell, and taking a conductive substrate as a cathode, wherein the conductive substrate is preferably used as an anode.
And (3) building a closed electric field induced deposition workstation, placing electrodes of the workstation at the left end and the right end of the electrolytic cell, applying voltage, and depositing on the surface of the cathode to form a fiber film layer.
Further, the deposition condition is 5-15V DC voltage, and the distance between the cathode and the anode is 8-12 mm. The capacity of the electrolytic cell is 2-4cm3The time is 4-6 min.
Further, in the step (3), the evaporation rate of the fluoride layer is
Figure BDA0003357199800000021
The thickness is 8-12 nm.
Further, in the step (3), the top electrode layer is evaporated on the lithium fluoride layer in vacuum through a mask plate of the circular hole array at the evaporation speed of
Figure BDA0003357199800000022
The thickness is 80-120nm, and the vacuum degree is 1 × 10-6-1×10-4Torr。
The invention also provides the celestite blue film composite material prepared by the preparation method.
The invention also provides an application of the celestite blue film composite material as an electric storage device.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. in the invention, dimethyl sulfoxide in the mixed solvent is used as a benign solvent of celestite blue, acetonitrile is used as a poor solvent of celestite blue, and celestite blue molecules consist of a cation conjugated framework, chlorine anions, hydroxyl and an amide group, so that the non-covalent bond effect between adjacent molecules, including hydrogen bonds, coulomb force and van der waals force, can be enhanced; secondly, the conjugated skeleton close to the plane can promote the pi-pi interaction in the material and induce the orientation of molecular accumulation; intramolecular charge transfer induces a memory effect based on the response of an electrical signal.
2. The film prepared by electric induction has excellent uniformity, continuity, large-area stability and flexibility, and the inside of the film has compact molecular accumulation, thereby effectively avoiding the problems caused by crack formation of crystal grains, overlarge gaps and irregular crystallization. The prepared electric memory array with controllable uniformity is beneficial to improving the electrical stability and performance reproducibility of the storage active layer, and provides important guarantee for the production and application of large-area organic thin films and flexible electronic devices.
Drawings
FIG. 1 is a schematic view of an electric field induced deposition workstation for the preparation of celestite blue nanofiber films;
FIG. 2 is an Atomic Force Microscope (AFM) image of a celestite blue nanofiber film;
FIG. 3 is a cross-sectional view of an atomic force microscope of a celestite blue nanofiber film;
FIG. 4 is a graph of the UV absorption spectrum of a celestite blue nanofiber film;
FIG. 5 is a schematic structural view of an electric memory of a celestite blue nanofiber film;
FIG. 6 is a graph of the electrical performance of an electrical memory of the "bottom electrode/celestite blue/top electrode" configuration;
FIG. 7 is a graph of electrical performance characteristic parameters of an electrical memory of the "bottom electrode/celestite blue/top electrode" configuration.
Description of reference numerals: 1-top electrode layer, 2-fluoride layer, 3-celestite blue film, 4-conductive substrate, 5-glass.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
Dissolving 2mg of azurite blue molecules in 1mL of dimethyl sulfoxide and 9mL of acetonitrile which are mixed, stirring for 12 hours, and fully dissolving to finally obtain a mixed solution which is used as a precursor for preparing the nanofiber membrane;
placing the prepared precursor solution in a pre-designed 3cm3In an electrolytic cell. Constructing a closed electric field induced deposition workstation, placing electrodes of the workstation at the left end and the right end of an electrolytic cell with the electrode spacing of 1mm, applying a voltage of 10V, and continuously depositing5 min; the celestite blue material is subjected to self-assembly in an electrolytic cell and is slowly deposited on the conductive indium tin oxide layer substrate 4 to obtain a uniform and compact organic nano fiber film layer; and then, taking the deposited film out of the electrolytic cell by using a pulling instrument, and flatly placing the film in a vacuum oven at 100 ℃ for drying to obtain the celestite blue film 3.
At 10-6Evaporating a lithium fluoride layer 2 on the surface of the nanofiber thin film layer under the condition of Torr vacuum degree at the evaporation speed of
Figure BDA0003357199800000032
The thickness was 10 nm. Then continuing to carry out vacuum evaporation on the metal Al electrode to the surface of the lithium fluoride layer through a mask plate with a circular hole array with uniform size at the evaporation speed
Figure BDA0003357199800000031
The thickness is 100nm, a top electrode layer 1 is obtained, and the top electrode layer is placed on glass 5, so that the celestite blue film composite material is obtained.
Example 2
Dissolving 4mg of azurite blue molecules in mixed 1.8mL of dimethyl sulfoxide and 18.2mL of acetonitrile, stirring for 8 hours, and fully dissolving to finally obtain a mixed solution serving as a precursor for preparing the nanofiber membrane;
placing the prepared precursor solution in a pre-designed 2cm3In an electrolytic cell. Building a closed electric field induced deposition workstation, placing electrodes of the workstation at the left end and the right end of an electrolytic cell, wherein the electrode distance is 8mm, then applying a voltage of 5V, and continuously depositing for 6 min; the celestite blue material is subjected to self-assembly in an electrolytic cell and is slowly deposited on a conductive indium tin oxide layer substrate to obtain a uniform and compact organic nanofiber thin film layer; and then, taking the deposited film out of the electrolytic cell by using a pulling instrument, and flatly placing the film in a vacuum oven at 100 ℃ for drying to obtain the celestite blue film.
At 10-4Evaporating a lithium fluoride layer on the surface of the nanofiber thin film layer under the condition of Torr vacuum degree at the evaporation speed of
Figure BDA0003357199800000041
The thickness was 8 nm. Then continuing to carry out vacuum evaporation on the metal Al electrode to the surface of the lithium fluoride layer through a mask plate with a circular hole array with uniform size at the evaporation speed
Figure BDA0003357199800000042
The thickness is 80nm, and the celestite blue film composite material is obtained.
Example 3
Dissolving 6mg of azurite blue molecules in 3.3mL of dimethyl sulfoxide and 26.7mL of acetonitrile which are mixed, stirring for 16 hours, and fully dissolving to finally obtain a mixed solution as a precursor for preparing the nanofiber membrane;
placing the prepared precursor solution in a pre-designed 4cm3In an electrolytic cell. Building a closed electric field induced deposition workstation, placing electrodes of the workstation at the left end and the right end of an electrolytic cell, wherein the electrode distance is 12mm, then applying a voltage of 15V, and continuously depositing for 4 min; the celestite blue material is subjected to self-assembly in an electrolytic cell and is slowly deposited on a conductive indium tin oxide layer substrate to obtain a uniform and compact organic nanofiber thin film layer; and then, taking the deposited film out of the electrolytic cell by using a pulling instrument, and flatly placing the film in a vacuum oven at 100 ℃ for drying to obtain the celestite blue film.
At 10-6Evaporating a lithium fluoride layer on the surface of the nanofiber thin film layer under the condition of Torr vacuum degree at the evaporation speed of
Figure BDA0003357199800000043
The thickness was 12 nm. Then continuing to carry out vacuum evaporation on the metal Al electrode to the surface of the lithium fluoride layer through a mask plate with a circular hole array with uniform size at the evaporation speed
Figure BDA0003357199800000044
The thickness is 120nm, and the celestite blue film composite material is obtained.
Example 4
Dissolving 6mg of azurite blue molecules in 3.3mL of dimethyl sulfoxide and 26.7mL of acetonitrile which are mixed, stirring for 16 hours, and fully dissolving to finally obtain a mixed solution as a precursor for preparing the nanofiber membrane;
placing the prepared precursor solution in a pre-designed 4cm3In an electrolytic cell. Building a closed electric field induced deposition workstation, placing electrodes of the workstation at the left end and the right end of an electrolytic cell, wherein the electrode distance is 12mm, then applying a voltage of 15V, and continuously depositing for 4 min; the celestite blue material is subjected to self-assembly in an electrolytic cell and is slowly deposited on a conductive zinc oxide layer substrate to obtain a uniform and compact organic nano fiber film layer; and then, taking the deposited film out of the electrolytic cell by using a pulling instrument, and flatly placing the film in a vacuum oven at 100 ℃ for drying to obtain the celestite blue film.
At 10-6Evaporating a magnesium fluoride layer on the surface of the nanofiber thin film layer under the condition of Torr vacuum degree at the evaporation speed of
Figure BDA0003357199800000045
The thickness was 12 nm. Then continuing to carry out vacuum evaporation on the metal Ag electrode to the surface of the magnesium fluoride layer through a mask plate with a circular hole array with uniform size at the evaporation speed
Figure BDA0003357199800000046
The thickness is 120nm, and the celestite blue film composite material is obtained.
Effect evaluation 1
The celestite blue molecules can realize self-assembly arrangement under the induction of an electric field and are orderly deposited on an electrode interface, as shown in figure 1. AFM images (fig. 2 and 3) of the azure blue nanofiber thin film show that the azure blue nanofibers were successfully prepared, the thin film showed good uniformity and continuity on a microscopic scale, and the width of a single nanofiber was about 100nm in a cross-sectional view.
In the uv absorption spectrum of the nanofiber film (fig. 4), the broader peak shape and red shift indicate that azure blue has stronger molecular forces and charge transfer effects in the fiber film state.
Effect evaluation 2
The performance test of the electric memory material with the structure of 'bottom electrode/fiber film/top electrode' comprises the following specific steps:
the prepared electrical memory material was tested at 25 ℃ and 30% humidity using a 4200-SCS semiconductor test system manufactured by Gishley, USA (Keithley). The current-voltage characteristic curve of the device is tested in a mode of applying 0 to +/-5V direct-current voltage scanning, and 50 groups of device units are tested continuously. And finally, counting the characteristic parameter distribution condition of the device performance under multiple tests so as to further investigate the electrical stability and the performance reproducibility of the electric memory material based on the nanofiber film.
From the voltage-current performance characterization of the memory device with the "bottom electrode/nanofiber thin film/top electrode" structure (fig. 6), it can be seen that the device exhibits similar binary resistance state changes based on two memory states of "0" and "1" under positive electric field scanning, and the current level of the device is changed from "1" to "0" by applying negative voltage, thus exhibiting volatile electrical memory characteristics.
According to the electric property characteristic parameter distribution characterization result (figure 7) of the electric memory material with the structure of the bottom electrode/celestite blue/top electrode, the threshold voltage distribution of the device based on the on state and the off state presents better normal distribution. The distribution range of the opening voltage is mainly concentrated on 1-2V, and the distribution range of the closing voltage is mainly distributed from-3.5V to-4.5V.
In conclusion, the celestite blue thin film composite material prepared by the method has a reliable application prospect in the field of electric memories.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. The preparation method of the celestite blue film composite material is characterized by comprising the following steps of:
(1) dissolving celestite blue in dimethyl sulfoxide, and adding acetonitrile to obtain a precursor solution;
(2) depositing the precursor solution on a conductive substrate to form a fiber film layer;
(3) and sequentially evaporating a fluoride layer and a top electrode layer on the surface of the fiber film layer to obtain the celestite blue film composite material.
2. The method according to claim 1, wherein in the step (1), the volume ratio of dimethyl sulfoxide to acetonitrile is 1: 8-10.
3. The method of claim 1, wherein in step (1), the concentration of celestite blue in the precursor solution is 0.1-0.3 mg/mL.
4. The production method according to claim 1, wherein the conductive substrate is an indium tin oxide layer substrate or a zinc oxide layer substrate;
the fluoride layer is a lithium fluoride layer or a magnesium fluoride layer;
the top electrode layer is a metal Au layer, an Ag layer or an Al layer.
5. The method according to any one of claims 1 to 4, wherein the step (2) is specifically carried out by: and putting the precursor solution into an electrolytic cell, applying voltage by taking a conductive substrate as a cathode, and depositing on the surface of the cathode to form a fiber film layer.
6. The method of claim 5, wherein the deposition condition is a DC voltage of 5-15V and the distance between the cathode and the anode is 8-12 mm.
7. The method according to claim 1, wherein in the step (3), the evaporation rate of the fluoride layer is set to be
Figure FDA0003357199790000011
The thickness is 8-12 nm.
8. The method of claim 1, wherein in step (3), the top electrode layer is evaporated onto the lithium fluoride layer at a rate of evaporation
Figure FDA0003357199790000012
The thickness is 80-120nm, and the vacuum degree is 1 × 10-6-1×10-4Torr。
9. A celestite blue thin film composite material prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the celestite blue thin film composite material of claim 9 as an electrical storage device.
CN202111355127.1A 2021-11-16 2021-11-16 Celestite blue film composite material and preparation method thereof Pending CN114122258A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114905674A (en) * 2022-06-02 2022-08-16 西南石油大学 Method for preparing aramid nano-fiber film through in-situ electrodeposition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114905674A (en) * 2022-06-02 2022-08-16 西南石油大学 Method for preparing aramid nano-fiber film through in-situ electrodeposition
CN114905674B (en) * 2022-06-02 2023-09-01 西南石油大学 Method for preparing aramid nanofiber film by in-situ electrodeposition

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